近日，中国海洋大学黄明华团队研究了缺陷驱动的金属有机框架逐步活化，实现工业级阴离子交换膜水电解。相关论文于2025年5月15日发表在《德国应用化学》杂志上。

金属有机骨架（MOFs）具有明确的金属活性位点和独特的配位环境，是近年来在析氧反应（OER）中建立精确构效关系的理想模型催化剂。然而，阐明动态反应条件的基本催化机制仍然具有挑战性，主要是由于OER过程中复杂的吸附行为和关键吸附物的跨步转移。

研究组提出了一种缺陷驱动的逐步激活策略，通过调整局部配位几何和电子构型之间的相互作用来精确控制缺陷Co基MOF（称为D/CoFc-MOF）的吸附行为。原位表征表明，D/CoFc-MOF在OER过程中经历了一个独特的阶梯活化过程，从原始MOF状态到中间a-FeOOH状态，最终到活性CoFeOOH相，这与传统的单步表面相转化明显不同。

理论计算表明，MOF衍生的缺陷CoFeOOH的活性Co位点与OOH*中间体之间的电子相互作用可以有效加强，从而克服高反应势垒，提高OER活性。D/CoFc-MOF阳极部署在阴离子交换膜电解中，在1.69 V下达到了1 A cm^-2的试验级电流密度，并稳定运行了300小时。该方法为设计易于动态相变的催化剂提供了基本的见解。

附：英文原文

Title: Defect-Driven Stepwise Activation of Metal–Organic Frameworks toward Industrial-Level Anion Exchange Membrane Water Electrolysis

Author: Jian Zhou, Shuai Qiu, Xianbiao Hou, Tengjia Ni, Canhui Zhang, Shuixing Dai, xingkun Wang, Guanghui Wang, Heqing Jiang, Minghua Huang

Issue&Volume: 2025-05-15

Abstract: Metal-organic frameworks (MOFs), featuring well-defined metal active sites and unique coordination environment, have recently emerged as ideal model catalysts for establishing precise structure-activity relationships in oxygen evolution reaction (OER). However, elucidating essential catalytic mechanisms responsible for dynamic reaction conditions remain challenging, primarily due to the complicated adsorption behavior and cross-step transfer of key adsorbates during OER.  Herein, we propose a defect-driven stepwise activation strategy to meticulously control the adsorption behavior for defective Co-based MOF (termed D/CoFc-MOF) through tailoring the interplay between local coordination geometry and electronic configuration. Operando characterizations reveal that D/CoFc-MOF undergoes a unique stepwise activation during OER, progressing from pristine MOF state to intermediate a-FeOOH state, and ultimately to active CoFeOOH phase, which markedly differs from conventional single-step surface phase conversion. Theoretical calculations demonstrate that the electronic interaction between the active Co sites and OOH* intermediates of MOF-derived defective CoFeOOH can be effectively strengthened, thereby overcoming the high reaction barrier and enhancing OER activity. The D/CoFc-MOF anode, deployed in anion exchange membrane water electrolysis, achieves industrial-scale current densities of 1 A cm-2 at 1.69 V and operates stably for 300 h. This approach provides a fundamental insight into designing catalysts prone to dynamic phase transitions.

DOI: 10.1002/anie.202503787

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202503787